Process for the dyeing of synthetic polyamide fibres and fabric from an acid dyebath containing an aminoxide



United States Patent 01 Ffice 3,524,205 Patented Aug. 18, 1970 US. Cl.8172 4 Claims ABSTRACT OF THE DISCLOSURE The process of dyeing syntheticpolyamide fibres or fabric, e.g. poly-caprolactam, in an acidic aqueousdyebath in the presence of an aminoxide, e.g.

/C H: C 12H25N O Ha The present invention relates to a process fordyeing synthetic polyamide fibres or materials containing such fibres inan acidic aqueous dyebath; more particularly it concerns a processwherein the dyeing is carried out in the presence of aminoxides whichcontain an alkyl radical with at least 8 to 20 carbon atoms or analkylaryl radical linked with the nitrogen atom directly or via bridgemembers.

Compounds of the following formulae can be used as aminoxides for theprocess of the present invention, for example:

In these formulae R stands for an alkyl radical with 8 to 20, preferably12 to 18, carbon atoms, R and R independently of one another, stand foran alkyl radical with 1 to 12 carbon atoms or for the grouping {-C HO),,H in which n denotes an integer from 1 to 20, R stands for an alkylradical with 8 to 20 carbon atoms or for an alkylaryl radical, R and Rindependently of one another, stand for alkyl radicals with 1 to 4carbon atoms, X stands for oxygen or sulphur, and Y stands for abivalent alkylene radical with 2 or 3 carbon atoms which may besubstituted by methyl or hydroxyl, while m de-- notes an integer from 1to 10.

Alkyl radicals represented by R are, for example, decyl, dodecyl,2,2-dimethyldecyl, isotridecyl, hexadecyl and octadecyl; alkyl radicalrepresented by R and R are, for example, methyl, ethyl, propyl, octyland dodecyl;

alkyl or alkylaryl radicals represented by R, are, for example, decyl,dodecyl, 2,2-dimethyldecyl, 2,2,4,6,6-pentamethyl-heptyl-(4),isotridecyl, hexadecyl, octadecyl, isooctyl-phenyl and isononyl-phenyl;and alkyl radical represented by R and R are, for example, methyl,ethyl, isopropyl and butyl, while Y stands, for example, for theradicals (CH (CH Aminoxides corresponding to the above Formula I whereinR and R stand for alkyl radicals, can be obtained, for example, bytreating the tertiary amines from which they are derived with hydrogenperoxide.

Aminoxides corresponding to the Formula I wherein R and/or R stand forthe grouping {-C H O) ,H, can be obtained, for example, by treating thereaction products of ethylene oxide on appropriate primary or secondaryamines with hydrogen peroxide.

Aminoxides corresponding to the Formula II wherein Y stands for (CH canbe obtained, for example, by preparing from the reaction product of 1mol ethylene oxide on 1 mol of an alcohol, mercaptan or alkylphenolcontaining the radical R the alkali metal or ammonium salts of theacidic sulphuric acid ester, reacting these with appropriate secondaryamines in the presence of strong bases and then treating the resultantether amines with hydrogen peroxide.

Compounds of the Formula II wherein Y stands for (CH or for CH -CH(CH)CH can be obtained, for example, by reacting alcohols, mercaptans oralkylphenols containing the radical R, with acrylonitrile ormethacrylonitrile, reducing the resultant cyanoethyl or cyanopropylethers to form the primary ether amines, converting these into tertiaryether amines by alkylation, and then treating the tertiary ether amineswith hydrogen peroxide.

Compounds of the Formula II wherein Y stands for -CH CH(OH)CH can beobtained, for example, by reacting alcohols, mercaptans or alkylphenolscontaining the radical R, with epichlorohydrin, reacting the resultantglycidyl ethers with appropriate secondary aliphatic amines and thentreating the resultant tertiary ether amines with hydrogen peroxide.

The compounds of the Formula III can be obtained according to analogousmethods by using, instead of the alcohols, mercaptans or alkylphenolscontaining the radical R themselves, the appropriate reaction productsthereof with ethylene oxide.

Dyestulfs which can be used in the process according to the inventionare, for example, substantive dyestufis, acid dyestuffs and 1:2 metalcomplex dyestuffs.

The necessary amounts of aminoxides can easily be established bypreliminary experiments; in general, 0.1 to 5 parts by weight aminoxideper 1 part by weight of dyestuff will prove sufiicient. Dyeing of thesynthetic polyamide fibres can then be carried out in the usual manner.

With the aid of the process according to the invention it is possible toobtain very level dyeings on synthetic polyamide fibres, for example,fibres made of polycaprolactam, of the polycondensation product ofhexamethylene diamine and adipic acid or of the polycondensation productof w-amino-undecanic acid, as well as on materials containing suchfibres, such as fabrics or knitted fabrics. This is surprising, becausethe risk of an uneven dyeing which exists when dyeing syntheticpolyamides, due to the differences in aflinity, titre and thread tensionwhich are always present, cannot be satisfactorily obviated by the useof levelling agents such as have hitherto been used for dyeing ofsynthetic fibres.

The following examples serve to illustrate the invention Without,however, limiting its scope; the parts given are parts by Weight.

EXAMPLE 1 0.05 part of the dyestuff Colour Index, 2nd edition, No.29,035 and 0.008 part aminoxide of the formula are dissolved in parts ofwater; in addition, 0.05 part of the dyestuif Colour Index No. 23,150and 0.131 part of the above aminoxide are dissolved in 5 parts of water,and 0.025 part of the dyestuff Colour Index No. 22,155 and 0.015 part ofthe above aminoxide are dissolved in 2.5 parts of water. The threesolutions are then stirred into 3000 parts of water which was adjustedwith 85% formic acid to a pH value of 3 and to which 0.5 part of theabove aminoxide had been added. 100 parts of knitted goods made ofpoly-e-caprolactam threads are introduced into the dvebath thus preparedand heated to 3040 C., the dyebath is heated to 90l00 C. in the courseof 30 minutes, and kept at this temperature for a further 30 to 60minutes. The knitted goods are finally rinsed in water and then dried. Avery level green dyeing of good fastness to light and wet processing isobtained.

The aminoxide used was prepared as follows:

342 parts of the reaction product of 3 mol ethylene oxide on 1 molisotridecyl alcohol were mixed dropwise at -20 C. with 127 partschlorosulphonic acid, the mixture was stirred for 1 hour at -30" C. andsubsequently added at 2035 C., while cooling, to a solution of 140 partssodium hydroxide in 600 parts of Water. The resultant reaction mixturewas subsequently mixed with 170 parts of a 40% aqueous dimethylaminesolution and heated in an autoclave at 160-l80 C. for 8 hours. Thereaction product was subjected to phase separation at 8090 C. The lowerphase was removed, the upper phase was stirred hot With 150 parts ofwater. The resultant mixture was again subjected to phase separation;the lower phase was removed, the upper phase was then freed from waterat 8090 C. in a vacuum. 111 parts of the tertiary ether amine soobtained were dissolved in 50 parts ethanol and mixed dropwise at 6065C. with 45 parts of hydrogen peroxide. The mixture was subsequentlystirred at the same temperature for 6 hours. The unreacted hydrogenperoxide was destroyed by suspending a platinum foil in the mixture. Theaminoxide formed Was then freed from ethanol and water in a vacuum at60-70 C.

EXAMPLE 2 0.5 part of the dyestuif Colour Index No. 23,150 and 1.6 partsof the aminoxide of the formula are dissolved in 50 parts of water; inaddition, 1 part of the dyestuff Colour Index No. 29,035 is mixed with0.2 part of the above aminoxide and the mixture is dissolved in 100parts of water. The two solutions are stirred into 2850 parts of waterwhich has been adjusted to a pH value of 3 by means of 85% formic acid.100 parts of knitted goods made of poly-e-caprolactam threads are thendyed in the dyebath so prepared in the manner described in Example 1. Alevel green dyeing is again obtained.

The aminoxide used was prepared as follows:

213 parts N,N-dimethyl-dodecylarnine were dissolved in 300 parts ethanoland mixed dropwise at 50-55 C.

N Rs 25 wherein R is an alkyl group of 8 to 20 carbon atoms;

R and R independently, are alkyl groups of 1 to 12 carbon atoms or {C HO), H in which n is an integer from 1 to 20;

R is an alkyl or an alkylaryl group of 8 to 20 carbon atoms;

R and R independently, are alkyl groups with 1 to 4 carbon atoms;

X is oxygen or sulphur; and

Y is an unsubstituted or a substituted bivalent alkylene radical with 2or 3 carbon atoms wherein the substituents are methyl or hydroxyl; and

m is an integer from 1 to 10.

2. The process of claim 1 wherein the the formula aminoxide has 3. Theprocess of claim 1 wherein the the formula 4. The process of claim 1wherein the the formula aminoxide has References Cited UNITED STATESPATENTS 2,074,380 3/1937 Flett 885 X 2,220,834 11/1940 Bruson et a1.8-85 X 2,940,815 6/1960 Taras 885 X GEORGE F. LESMES, Primary ExaminerT. J. HERBERT, JR., Assistant Examiner US. Cl. X.R. 8-173, 178

Patent No.

Inventor(s) Column Line 4 Claim 1 (SEAL) Attest:

Edward M- Flm J UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONWerner Langmann, et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Error "45 parts" should read 125 parts Dated August 18, 1970 iElsQ i-ZJMil FALEE WILLIAM E- SGHUYLER, JR.

Oomiasionar of Patents AnwtIngOffioer ORM PO-105O (10-69 USCOMM-DC60376-P69 9 u s, GOVERHMENY PRINTING OFFICE I969 0-366-334

